Abstract

Time-resolved coherent anti-Stokes Raman-scattering (CARS) measurements are carried out to study the interaction between xenon atom and iodine molecule in a solid krypton matrix. Interference between the CARSpolarizations of the “free” and complexed iodine molecules is observed, while the quantum beats of the complex are not detected due to low concentration. Vibrational analysis based on the polarization beats yields accurate molecular constants for the complex. The harmonic frequency of the complex is found to be redshifted by when compared to the free , whereas the anharmonicity is approximately the same. The dephasing rate of the complex is found to be somewhat higher than that of the free iodine molecule in solid Kr, showing that the complexation affects dephasing, although not dramatically. Molecular dynamics simulations are carried out to find the conformation of the complex, and wave packet simulations are used to reproduce the CARS signal to confirm the assignments of the observed beatings as quantum and polarization beats. The results show that the polarization beats are a useful tool for investigating weak interactions in condensed phase.

Received 16 June 2006Accepted 08 September 2006Published online 23 October 2006

Acknowledgments:

This work was supported by the Academy of Finland (Decision Nos. 105684 and 110952). The authors thank Pasi Myllyperkiö and Jukka Aumanen for their help in the measurements. Professor Henrik Kunttu and Professor Jouko Korppi-Tommola are thanked for their support to this work. Professor V. A. Apkarian is thanked for many fruitful discussions.